Lithium extraction with porous ion exchange beads

ABSTRACT

The present invention relates to the extraction of lithium from liquid resources such as natural and synthetic brines, leachate solutions from minerals, and recycled products.

BACKGROUND OF THE INVENTION

Lithium is an essential element for high-energy rechargeable batteriesand other technologies. Lithium can be found in a variety of liquidsolutions, including natural and synthetic brines and leachate solutionsfrom minerals and recycled products.

SUMMARY OF THE INVENTION

Lithium can be extracted from liquid resources using an ion exchangeprocess based on inorganic ion exchange materials. Inorganic ionexchange materials absorb lithium ions from a liquid resource whilereleasing hydrogen ions, and then elute lithium ions in acid whileabsorbing hydrogen ions. The ion exchange process can be repeated toextract lithium ions from a liquid resource and yield a concentratedlithium ion solution. The concentrated lithium ion solution can befurther processed into chemicals for the battery industry or otherindustries.

An aspect described herein is a method of making porous ion exchangebeads, comprising: combining and mixing ion exchange particles thatreversibly exchange lithium and hydrogen, a matrix material, and afiller material to make a mixture; forming the mixture into beads;optionally heating the beads; and removing a portion or essentially allof the filler material to make porous ion exchange beads. In someembodiments, the combining and mixing are done using dry powders. Insome embodiments, the combining and mixing are done using one or moresolvents and the mixture is a slurry. In some embodiments, the formingis done using a mechanical press. In some embodiments, the forming isdone by injecting the slurry into a liquid. In some embodiments, theheating is sufficient to melt or sinter the matrix material. In someembodiments, the removing is done by dissolving the filler materialusing water, an aqueous solution, an acid, a brine, an alcohol, orcombinations thereof. In some embodiments, the removing is done byheating the beads sufficient to decompose the filler material to gaseousparticles or decomposition products.

An aspect described herein is a method of making a porous ion exchangebead for extraction of lithium from a liquid resource comprising:forming a precursor bead wherein the precursor bead comprises an ionexchange material, a matrix material and a filler material; and removingat least a portion of the filler material to produce the porous ionexchange bead. In some embodiments, essentially all of the fillermaterial is removed.

In some embodiments, the ion exchange material is selected from coatedion exchange particles, uncoated ion exchange particles, andcombinations thereof. In some embodiments, the coated ion exchangeparticles comprise an ion exchange material and a coating material.

In some embodiments, the coating material of the coated ion exchangeparticles comprises a carbide, a nitride, an oxide, a phosphate, afluoride, a polymer, carbon, a carbonaceous material, or combinationsthereof. In some embodiments, the coating material of the coated ionexchange particles is selected from the group consisting of TiO₂, ZrO₂,MoO₂, SnO₂, Nb₂O₅, Ta₂O₅, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂SiO₃, Li₂MnO₃,Li₂MoO₃, LiNbO₃, LiTaO₃, AlPO₄, LaPO₄, ZrP₂O₇, MOP₂O₇, MO₂P₃O₁₂, BaSO₄,AlF₃, SiC, TiC, ZrC, Si₃N₄, ZrN, BN, carbon, graphitic carbon, amorphouscarbon, hard carbon, diamond-like carbon, solid solutions thereof, andcombinations thereof. In some embodiments, the coating material of thecoated ion exchange particles is selected from the group consisting ofpolyethylene, low density polyethylene, high density polyethylene,polypropylene, polyphenylene sulfide, polyester,polytetrafluoroethylene, types of polyamide, polyether ether ketone,polysulfone, polyvinylidene difluoride, poly (4-vinylpyridine-co-styrene), polystyrene, polybutadiene, acrylonitrilebutadiene styrene, polyvinyl chloride, polyvinylidene dichloride,ethylene tetrafluoroethylene polymer, poly(chlorotrifluoroethylene),ethylene chlorotrifluoro ethylene, polyvinyl fluoride, fluorinatedethylene-propylene, perfluorinated elastomer,chlorotrifluoroethylenevinylidene fluoride, perfluoropolyether,perfluorosulfonic acid, polyethylene oxide, polyethylene glycol, sodiumpolyacrylate, polyethylene-block-poly(ethylene glycol),polyacrylonitrile, polychloroprene (neoprene), polyvinyl butyral,expanded polystyrene, polydivinylbenzene,tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer, copolymers thereof, and combinations thereof.

In some embodiments, the ion exchange material of the coated ionexchange particles comprises an oxide, a phosphate, an oxyfluoride, afluorophosphate, or combinations thereof. In some embodiments, the ionexchange material of the coated ion exchange particles is selected fromthe group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂, Li₂TiO₃, Li₂MnO₃, Li₂SnO₃,LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂, LiTiO₂, Li₄TiO₄,Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄, Li₂CuP₂O₇, Al(OH)₃,LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O, TiO₂.xSb₂O₅.yH₂O, solid solutionsthereof, and combinations thereof, wherein x is from 0.1-10; and y isfrom 0.1-10.

In some embodiments, the uncoated ion exchange particles comprise an ionexchange material. In some embodiments, the ion exchange material of theuncoated ion exchange particles comprises an oxide, a phosphate, anoxyfluoride, a fluorophosphate, or combinations thereof. In someembodiments, the ion exchange material of the uncoated ion exchangeparticles is selected from the group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂,Li₂TiO₃, Li₂MnO₃, Li₂SnO₃, LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂,LiTiO₂, Li₄TiO₄, Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄,Li₂CuP₂O₇, Al(OH)₃, LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O,TiO₂.xSb₂O₅.yH₂O, solid solutions thereof, and combinations thereof,wherein x is from 0.1-10; and y is from 0.1-10.

In some embodiments, the matrix material comprises a polymer, an oxide,a phosphate, or combinations thereof. In some embodiments, the matrixmaterial is selected from the group consisting of polyvinyl fluoride,polyvinylidene difluoride, polyvinyl chloride, polyvinylidenedichloride, polyethylene, polypropylene, polyphenylene sulfide,polytetrafluoroethylene, sulfonated polytetrafluoroethylene,polystyrene, polydivinylbenzene, polybutadiene,poly-ethylene-tetrafluoroethyelene, polyacrylonitrile, sulfonatedpolymer, carboxylated polymer,tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer, copolymers thereof, and combinations thereof.

In some embodiments, the filler material is a salt, a chloride salt,sodium chloride, a sulfate salt, a carbonate salt, a nitrate salt, analkali metal salt, an alkali earth metal salt, an organic material, apolymer, an aqueous liquid, an organic liquid, a liquid mixture, orcombinations thereof. In some embodiments, the filler material isremoved by treating the precursor bead with a solvent. In someembodiments, the solvent dissolves the filler material in the precursorbead. In some embodiments, the solvent is selected from the groupconsisting of water, ethanol, iso-propyl alcohol, acetone, andcombinations thereof. In some embodiments, the filler material isremoved by sublimation or evaporation optionally involving subjectingthe precursor bead to heat, vacuum, air, or combinations thereof. Insome embodiments, the heat decomposes the filler material.

In some embodiments, the porous ion exchange bead has an averagediameter of less than about 10 μm. In some embodiments, the porous ionexchange bead has an average diameter of less than about 100 μm. In someembodiments, the porous ion exchange bead has an average diameter ofless than about 1000 μm. In some embodiments, the porous ion exchangebead has an average diameter of greater than about 1000 μm.

An aspect described herein is a porous ion exchange bead comprising ionexchange material and a matrix material, wherein the porous ion exchangebead is prepared by a process comprising the steps of: combining the ionexchange material and the matrix material with a filler material toproduce a precursor bead; and removing the filler material.

In some embodiments, the ion exchange material is selected from coatedion exchange particles, uncoated ion exchange particles, andcombinations thereof. In some embodiments, the coated ion exchangeparticles comprise an ion exchange material and a coating material.

In some embodiments, the coating material of the coated ion exchangeparticles comprises a carbide, a nitride, an oxide, a phosphate, afluoride, a polymer, carbon, a carbonaceous material, or combinationsthereof. In some embodiments, the coating material of the coated ionexchange particles is selected from the group consisting of TiO₂, ZrO₂,MoO₂, SnO₂, Nb₂O₅, Ta₂O₅, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂SiO₃, Li₂MnO₃,Li₂MoO₃, LiNbO₃, LiTaO₃, AlPO₄, LaPO₄, ZrP₂O₇, MOP₂O₇, MO₂P₃O₁₂, BaSO₄,AlF₃, SiC, TiC, ZrC, Si₃N₄, ZrN, BN, carbon, graphitic carbon, amorphouscarbon, hard carbon, diamond-like carbon, solid solutions thereof, andcombinations thereof. In some embodiments, the coating material of thecoated ion exchange particles is selected from the group consisting ofpolyethylene, low density polyethylene, high density polyethylene,polypropylene, polyphenylene sulfide, polyester,polytetrafluoroethylene, types of polyamide, polyether ether ketone,polysulfone, polyvinylidene difluoride, poly (4-vinylpyridine-co-styrene), polystyrene, polybutadiene, acrylonitrilebutadiene styrene, polyvinyl chloride, polyvinylidene dichloride,ethylene tetrafluoroethylene polymer, poly(chlorotrifluoroethylene),ethylene chlorotrifluoro ethylene, polyvinyl fluoride, fluorinatedethylene-propylene, perfluorinated elastomer,chlorotrifluoroethylenevinylidene fluoride, perfluoropolyether,perfluorosulfonic acid, polyethylene oxide, polyethylene glycol, sodiumpolyacrylate, polyethylene-block-poly(ethylene glycol),polyacrylonitrile, polychloroprene (neoprene), polyvinyl butyral,expanded polystyrene, polydivinylbenzene,tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer, copolymers thereof, and combinations thereof.

In some embodiments, the ion exchange material of the coated ionexchange particles comprises an oxide, a phosphate, an oxyfluoride, afluorophosphate, or combinations thereof. In some embodiments, the ionexchange material of the coated ion exchange particles is selected fromthe group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂, Li₂TiO₃, Li₂MnO₃, Li₂SnO₃,LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂, LiTiO₂, Li₄TiO₄,Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄, Li₂CuP₂O₇, Al(OH)₃,LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O, TiO₂.xSb₂O₅.yH₂O, solid solutionsthereof, and combinations thereof, wherein x is from 0.1-10; and y isfrom 0.1-10.

In some embodiments, the uncoated ion exchange particles comprise an ionexchange material. In some embodiments, the ion exchange material of theuncoated ion exchange particles comprises an oxide, a phosphate, anoxyfluoride, a fluorophosphate, or combinations thereof. In someembodiments, the ion exchange material of the uncoated ion exchangeparticles is selected from the group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂,Li₂TiO₃, Li₂MnO₃, Li₂SnO₃, LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂,LiTiO₂, Li₄TiO₄, Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄,Li₂CuP₂O₇, Al(OH)₃, LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O,TiO₂.xSb₂O₅.yH₂O, solid solutions thereof, and combinations thereof,wherein x is from 0.1-10; and y is from 0.1-10

In some embodiments, the matrix material comprises a polymer, an oxide,a phosphate, or combinations thereof. In some embodiments, the matrixmaterial is selected from the group consisting of polyvinyl fluoride,polyvinylidene difluoride, polyvinyl chloride, polyvinylidenedichloride, polyethylene, polypropylene, polyphenylene sulfide,polytetrafluoroethylene, sulfonated polytetrafluoroethylene,polystyrene, polydivinylbenzene, polybutadiene, sulfonated polymer,carboxylated polymer, poly-ethylene-tetrafluoroethyelene,polyacrylonitrile,tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer, copolymers thereof, and combinations thereof.

In some embodiments, the filler material is a salt, a chloride salt,sodium chloride, a sulfate salt, a carbonate salt, a nitrate salt, analkali salt, an alkali earth salt, an organic material, a polymer, anaqueous liquid, an organic liquid, a liquid mixture, or combinationsthereof. In some embodiments, the filler material is removed by treatingthe precursor bead with a solvent. In some embodiments, the solventdissolves the filler material in the precursor bead. In someembodiments, the solvent is selected from the group consisting of water,ethanol, iso-propyl alcohol, acetone, and combinations thereof. In someembodiments, the filler material is removed by sublimation orevaporation optionally involving subjecting the precursor bead to heat,vacuum, air, or combinations thereof. In some embodiments, the heatdecomposes the filler material.

An aspect described herein is a method of extracting lithium from aliquid resource, comprising: contacting the porous ion exchange bead asdescribed herein with a liquid resource to produce a lithiated porousion exchange bead; and treating the lithiated porous ion exchange beadwith an acid solution to produce a salt solution comprising lithiumions.

In some embodiments, the liquid resource is a natural brine, a dissolvedsalt flat, seawater, concentrated seawater, a desalination effluent, aconcentrated brine, a processed brine, waste brine from abromine-extraction process, an oilfield brine, a liquid from an ionexchange process, a liquid from a solvent extraction process, asynthetic brine, a leachate from an ore or combination of ores, aleachate from a mineral or combination of minerals, a leachate from aclay or combination of clays, a leachate from recycled products, aleachate from recycled materials, or combinations thereof.

In some embodiments, the acid solution comprises hydrochloric acid,sulfuric acid, phosphoric acid, hydrobromic acid, chloric acid,perchloric acid, nitric acid, formic acid, acetic acid, or combinationsthereof. In some embodiments, the method is conducted in a column, avessel, or a stirred tank reactor.

INCORPORATION BY REFERENCE

All publications, patents, and patent applications mentioned in thisspecification are herein incorporated by reference to the same extent asif each individual publication, patent, or patent application wasspecifically and individually indicated to be incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

The novel features of the invention are set forth with particularity inthe appended claims. A better understanding of the features andadvantages of the present invention will be obtained by reference to thefollowing detailed description that sets forth illustrative embodiments,in which the principles of the invention are utilized, and theaccompanying drawings of which:

FIG. 1 depicts a porous bead containing ion exchange particles, matrixmaterial, and pores formed by removing filler material.

FIG. 2 depicts a coated ion exchange particle with a Li₄Mn₅O₁₂ ionexchange material and a ZrO₂ coating protecting the particle surface.

FIG. 3 depicts an ion exchange column loaded with porous polymer beadscontaining ion exchange particles, a matrix material, and pores formedby removing filler material.

FIG. 4 depicts a stirred tank reactor comprising a compartment forcontaining porous beads in the compartment while allowing solutions todrain out of the bottom of the compartment and out of the bottom of thestirred tank reactor.

DETAILED DESCRIPTION OF THE INVENTION

Lithium is an essential element for batteries and other technologies.Lithium is found in a variety of liquid resources, including natural andsynthetic brines and leachate solutions from minerals, clays, andrecycled products. Lithium can be extracted from such liquid resourcesusing an ion exchange process based on inorganic ion exchange materials.These inorganic ion exchange materials absorb lithium from a liquidresource while releasing hydrogen, and then elute lithium in acid whileabsorbing hydrogen. This ion exchange process can be repeated to extractlithium from a liquid resource and yield a concentrated lithiumsolution. The concentrated lithium solution can be further processedinto chemicals for the battery industry or other industries.

Ion exchange materials can be formed into small particles, whichtogether constitute a fine powder. Small particle size is required tominimize the diffusion distance that lithium must travel into the coreof the ion exchange particles. In some cases, these particles may becoated with protective surface coatings to minimize dissolution of theion exchange materials while allowing efficient transfer of lithium andhydrogen to and from the particles, as disclosed in U.S. provisionalapplication 62/421,934, filed on Nov. 14, 2016, entitled “LithiumExtraction with Coated Ion Exchange Particles,” and incorporated in itsentirety by reference.

One major challenge for lithium extraction using inorganic ion exchangeparticles is the loading of the particles into an ion exchange vessel insuch a way that brine and acid can be pumped efficiently through thecolumn with minimal clogging and minimal loss of particles from thevessel. The materials can be formed into beads, and the beads can beloaded into the vessel. This bead loading creates void spaces betweenthe particles, and these void spaces facilitate movement of brinethroughout the particles. The beads hold the ion exchange particles inplace and prevent loss of particles the particles from the vessel. Whenthe materials are formed into beads, the penetration of brine and acidsolutions into the beads may become slow and challenging. A slow rate ofconvection and diffusion of the acid and brine solutions into the beadslows the kinetics of lithium absorption and release. Such slow kineticscan create problems for operation of an ion exchange system. Slowkinetics can require slow pumping rates through the vessel. Slowkinetics can also lead to low lithium recovery from the brine andinefficient use of acid to elute the lithium.

The present invention includes a method for creating porous ion exchangebeads with networks of pores that facilitate the transport into thebeads of solutions that are pumped into an ion exchange vessel. Porenetworks can be strategically controlled to provide fast and distributedaccess for the brine and acid solutions to penetrate into the bead anddeliver lithium and hydrogen to the ion exchange particles. One exampleof a porous ion exchange bead is shown in FIG. 1 .

The present method for creating ion exchange beads involves mixing ofion exchange particles, a matrix material, and a filler material. Thesecomponents are mixed and formed into a bead. Then, the filler materialis removed from the bead to leave behind pores. The filler material isdispersed in the bead in such a way to leave behind a pore structurethat enables transport of lithium and hydrogen with fast kinetics. Thismethod may involve multiple ion exchange materials, multiple polymermaterials, and multiple filler materials.

Another major challenge for lithium extraction using inorganic ionexchange materials is dissolution and degradation of the materials,especially during lithium elution in acid but also during lithium uptakein liquid resources. To yield a concentrated lithium solution from theion exchange process, it is desirable to use a concentrated acidsolution to elute the lithium. However, concentrated acid solutionsdissolve and degrade inorganic ion exchange materials, which decreasesthe performance and lifespan of the materials. Therefore, the porous ionexchange beads may contain coated ion exchange particle for lithiumextraction that are comprised of an ion exchange material and a coatingmaterial protecting the particle surface. The coating protects the ionexchange material from dissolution and degradation during lithiumelution in acid, during lithium uptake from a liquid resource, andduring other aspects of an ion exchange process. This coated particleenables the use of concentrated acids in the ion exchange process toyield concentrated lithium solutions. One example of a coated ionexchange particle is shown in FIG. 2 .

In this invention, the ion exchange material is selected for highlithium absorption capacity, high selectivity for lithium in a liquidresource relative to other ions such as sodium and magnesium, stronglithium uptake in liquid resources including those with lowconcentrations of lithium, facile elution of lithium with a small excessof acid, and fast ionic diffusion. A coating material may be selected toprotect the particle from dissolution and chemical degradation duringlithium recovery in acid and also during lithium uptake in variousliquid resources. A coating material may also be selected to facilitatediffusion of lithium and hydrogen between the particles and the liquidresources, to enable adherence of the particles to a structural support,and to suppress structural and mechanical degradation of the particles.

The porous ion exchange beads may be loaded into an ion exchange vesselwith a fixed, moving, or fluidized bed. One example of an ion exchangecolumn is shown in FIG. 3 . The ion exchange vessel directs liquids topercolate around and through the ion exchange beads, therebyfacilitating ion exchange between the particles and the liquid resource.In some embodiments, the porous ion exchange beads may be mixed with aliquid resource to absorb lithium and then recovered through filtration,gravimetric separation, or other means.

When the porous ion exchange beads are used in an ion exchange vessel,the liquid resource containing lithium is pumped into the ion exchangevessel so that the ion exchange particles absorb lithium from the liquidresource while releasing hydrogen. After the beads have absorbed lithiumand the liquid resource has been removed from the vessel, an acidsolution is pumped into the vessel so that the particles release lithiuminto the acid solution while absorbing hydrogen. The vessel may beoperated in co-flow mode with the liquid resource and acid solutionalternately flowing through the vessel in the same direction, or thevessel may be operated in counter-flow mode with a liquid resource andacid solution alternately flowing through the vessel in oppositedirections. The vessel may be operated in a mode that is batch,semi-continuous, or continuous. Between flows of the liquid resource andthe acid solution, the column may be treated or washed with water orother solutions for purposes such as adjusting pH in the column orremoving potential contaminants. The beads may form a fixed or movingbed, and the moving bed may move in counter-current to the brine andacid flows. The beads may be moved between multiple vessels with movingbeds where different vessels are used for brine, acid, water, or otherflows. Before or after the liquid resource flows into the vessel, the pHof the liquid may be adjusted with NaOH or other chemicals to facilitatethe ion exchange reaction as well as handling or disposal of the spentliquid resource. Before or after the liquid resource flows into thevessel, the liquid resource may be subjected to other processesincluding other ion exchange processes, solvent extraction, evaporation,chemical treatment, or precipitation to remove lithium, to remove otherchemical species, or to otherwise treat the brine.

When the ion exchange particles are treated with acid, a lithiumsolution is produced. This lithium solution may be further processed toproduce lithium chemicals. These lithium chemicals may be supplied foran industrial application.

In some embodiments, an ion exchange material is selected from thefollowing list: an oxide, a phosphate, an oxyfluoride, afluorophosphate, or combinations thereof. In some embodiments, an ionexchange material is selected from the following list: Li₄MnO₁₂,Li₄Ti₅O₁₂, Li₂MO₃ (M=Ti, Mn, Sn), LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiMO₂(M=Al, Cu, Ti), Li₄TiO₄, Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄,Li₂CuP₂O₇, Al(OH)₃, LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O,TiO₂.xSb₂O₅.yH₂O, solid solutions thereof, or combinations thereof. Insome embodiments, an ion exchange material is selected from thefollowing list: Li₄Mn₅O₁₂, Li₄Ti₅O₁₂, Li_(1.6)Mn_(1.6)O₄, Li₂MO₃ (M=Ti,Mn, Sn), LiFePO₄, solid solutions thereof, or combinations thereof. Insome embodiments, the ion exchange material comprises Li₄Mn₅O₁₂. In someembodiments, the ion exchange material is Li₄Mn₅O₁₂.

In some embodiments, a coating material for protecting the surface ofthe ion exchange material is selected from the following list: acarbide, a nitride, an oxide, a phosphate, a fluoride, a polymer,carbon, a carbonaceous material, or combinations thereof. In someembodiments, a coating material is selected from the following list:TiO₂, ZrO₂, MoO₂, SnO₂, Nb₂O₅, Ta₂O₅, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂SiO₃,Li₂MnO₃, Li₂MoO₃, LiNbO₃, LiTaO₃, AlPO₄, LaPO₄, ZrP₂O₇, MoP₂O₇,MO₂P₃O₁₂, BaSO₄, AlF₃, SiC, TiC, ZrC, Si₃N₄, ZrN, BN, carbon, graphiticcarbon, amorphous carbon, hard carbon, diamond-like carbon, solidsolutions thereof, or combinations thereof. In some embodiments, acoating material is selected from the following list: polyvinylfluoride, polyvinylidene difluoride, polyvinyl chloride, polyvinylidenedichloride, polyethylene, polypropylene, polyphenylene sulfide,polytetrafluoroethylene, polytetrofluoroethylene, sulfonatedpolytetrofluoroethylene, polystyrene, polydivinylbenzene, polybutadiene,poly-ethylene-tetrafluoroethyelene, polyacrylonitrile, sulfonatedpolymer, carboxylated polymer, Nafion, copolymers thereof, andcombinations thereof. In some embodiments, a coating material isselected from the following list: TiO₂, ZrO₂, MoO₂, SiO₂, Li₂TiO₃,Li₂ZrO₃, Li₂SiO₃, Li₂MnO₃, LiNbO₃, AlF₃, SiC, Si₃N₄, graphitic carbon,amorphous carbon, diamond-like carbon, or combinations thereof. In someembodiments, the coating material is TiO₂, SiO₂ or ZrO₂. In a furtheraspect, a coating material comprises a chloro-polymer, a fluoro-polymer,a chloro-fluoro-polymer, a hydrophilic polymer, a hydrophobic polymer,co-polymers thereof, mixtures thereof, or combinations thereof. In afurther aspect, a coating material comprises a co-polymer, a blockco-polymer, a linear polymer, a branched polymer, a cross-linkedpolymer, a heat-treated polymer, a solution processed polymer,co-polymers thereof, mixtures thereof, or combinations thereof. In afurther aspect, a coating material comprises polyethylene, low densitypolyethylene, high density polyethylene, polypropylene, polyphenylenesulfide, polyester, polytetrafluoroethylene (PTFE), types of polyamide,polyether ether ketone (PEEK), polysulfone, polyvinylidene difluoride(PVDF), poly (4-vinyl pyridine-co-styrene) (PVPCS), polystyrene (PS),polybutadiene, acrylonitrile butadiene styrene (ABS), polyvinyl chloride(PVC), polyvinylidene dichloride, ethylene tetrafluoroethylene polymer(ETFE), poly(chlorotrifluoroethylene) (PCTFE), ethylene chlorotrifluoroethylene (Halar), polyvinylfluoride (PVF), fluorinatedethylene-propylene (FEP), perfluorinated elastomer,chlorotrifluoroethylenevinylidene fluoride (FKM), perfluoropolyether(PFPE), perfluorosulfonic acid (Nafion©), polyethylene oxide,polyethylene glycol, sodium polyacrylate,polyethylene-block-poly(ethylene glycol), polyacrylonitrile (PAN),polychloroprene (neoprene), polyvinyl butyral (PVB), expandedpolystyrene (EPS), polydivinylbenzene, co-polymers thereof, mixturesthereof, or combinations thereof. In a further aspect, a coatingmaterial comprises polyvinylidene difluoride (PVDF), polyvinyl chloride(PVC), ethylene chlorotrifluoro ethylene (Halar), poly (4-vinylpyridine-co-styrene) (PVPCS), polystyrene (PS), acrylonitrile butadienestyrene (ABS), expanded polystyrene (EPS), polyphenylene sulfide,sulfonated polymer, carboxylated polymer, other polymers, co-polymersthereof, mixtures thereof, or combinations thereof. In a further aspect,a coating is deposited onto an ion exchange particle by dry mixing,mixing in solvent, emulsion, extrusion, bubbling one solvent intoanother, casting, heating, evaporating, vacuum evaporation, spraydrying, vapor deposition, chemical vapor deposition, microwaving,hydrothermal synthesis, polymerization, co-polymerization,cross-linking, irradiation, catalysis, foaming, other depositionmethods, or combinations thereof. In a further aspect, a coating isdeposited using a solvent comprising n-methyl-2-pyrrolidone, dimethylsulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methylethyl ketone, ethanol, acetone, other solvents, or combinations thereof.

In some embodiments, the ion exchange particles may have an averagediameter that is selected from the following list: less than 10 nm, lessthan 100 nm, less than 1,000 nm, less than 10,000 nm, less than 100,000nm, or less than 500,000 nm. In some embodiments, the ion exchangeparticles may have an average diameter that is selected from thefollowing list: greater than 10,000 nm, greater than 100,000 nm, orgreater than 1,000,000 nm. In some embodiments, the ion exchangeparticles may have an average size that is selected from the followinglist: less than 200 nm, less than 2,000 nm, or less than 20,000 nm.

In some embodiments, the ion exchange particles may be secondaryparticles comprised of smaller primary particles that may have anaverage diameter selected from the following list: less than 10 nm, lessthan 100 nm, less than 1,000 nm, or less than 10,000 nm. In someembodiments, the ion exchange particles may be secondary particlescomprised of smaller primary particles that may have an average diametergreater than 10,000 nm or greater than 100,000 nm.

In some embodiments, the ion exchange particles have a coating materialwith a thickness selected from the following list: less than 1 nm, lessthan 10 nm, less than 100 nm, less than 1,000 nm, or less than 20,000nm. In some embodiments, the ion exchange particles have a coatingmaterial with a thickness selected from the following list: greater than1,000 nm, greater than 10,000 nm, or greater than 100,000 nm. In someembodiments, the coating material has a thickness selected from thefollowing list: less than 1 nm, less than 10 nm, or less than 100 nm.

In some embodiments, the ion exchange material and a coating materialmay form one or more concentration gradients where the chemicalcomposition of the particle ranges between two or more compositions. Insome embodiments, the ion exchange materials and the coating materialsmay form a concentration gradient that extends over a thickness selectedfrom the following list: less than 1 nm, less than 10 nm, less than 100nm, less than 1,000 nm, less than 10,000 nm, or less than 100,000 nm. Insome embodiments, the coating material may be similar in composition tothe ion exchange material. In some embodiments, the coating material maybe identical in composition to the ion exchange material but with one ormore elements doped into the coating material. In some embodiments, thecoating material may comprise a modified version of the ion exchangematerial. In some embodiments, the coating material may compriseLi₄Mn₅O₁₂, Li₄Ti₅O₁₂, Li₂MO₃ (M=Ti, Mn, Sn), LiMn₂O₄,Li_(1.6)Mn_(1.6)O₄, LiMO₂ (M=Al, Cu, Ti), Li₄TiO₄, Li₇Ti₁₁O₂₄, Li₃VO₄,Li₂Si₃O₇, LiFePO₄, LiMnPO₄, Li₂CuP₂O₇, Al(OH)₃, LiCl.xAl(OH)₃.yH₂O,SnO₂.xSb₂O₅.yH₂O, TiO₂.xSb₂O₅.yH₂O, solid solutions thereof, orcombinations thereof. In some embodiments, the coating material may bedoped with elements from the following list: Ti, Zr, Si, V, B, Al, orMg. In some embodiments the doping may extend over a thickness selectedfrom the following list: greater than 1 nm, greater than 10 nm, greaterthan 100 nm, greater than 1 micron, greater than 10 microns, or greaterthan 100 microns.

In some embodiments, the ion exchange material is synthesized by amethod selected from the following list: hydrothermal, solvothermal,sol-gel, solid state, molten salt flux, ion exchange, microwave, ballmilling, precipitation, or vapor deposition. In some embodiments, theion exchange material is synthesized by a method selected from thefollowing list: hydrothermal, solid state, or microwave.

In some embodiments, a coating material is deposited by a methodselected from the following list: chemical vapor deposition, atomiclayer deposition, physical vapor deposition, hydrothermal, solvothermal,sol-gel, solid state, molten salt flux, ion exchange, microwave, wetimpregnation, precipitation, titration, aging, ball milling, orcombinations thereof. In some embodiments, the coating material isdeposited by a method selected from the following list: chemical vapordeposition, hydrothermal, titration, solvothermal, wet impregnation,sol-gel, precipitation, microwave, or combinations thereof.

In some embodiments, a coating material is deposited with physicalcharacteristics selected from the following list: crystalline,amorphous, full coverage, partial coverage, uniform, non-uniform, orcombinations thereof.

In some embodiments, multiple coatings may be deposited on the ionexchange material in an arrangement selected from the following list:concentric, patchwork, or combinations thereof.

In some embodiments, the matrix is selected from the following list: apolymer, an oxide, a phosphate, or combinations thereof. In someembodiments, a structural support is selected from the following list:polyvinyl fluoride, polyvinylidene difluoride, polyvinyl chloride,polyvinylidene dichloride, polyethylene, polypropylene, polyphenylenesulfide, polytetrafluoroethylene, polytetrofluoroethylene, sulfonatedpolytetrofluoroethylene, polystyrene, polydivinylbenzene, polybutadiene,poly-ethylene-tetrafluoroethyelene, polyacrylonitrile, sulfonatedpolymer, carboxylated polymer, Nafion, copolymers thereof, andcombinations thereof. In some embodiments, a structural support isselected from the following list: polyvinylidene difluoride, polyvinylchloride, sulfonated polytetrofluoroethylene, polystyrene,polydivinylbenzene, copolymers thereof, or combinations thereof. In someembodiments, a structural support is selected from the following list:titanium dioxide, zirconium dioxide, silicon dioxide, solid solutionsthereof, or combinations thereof. In some embodiments, the matrixmaterial is selected for thermal resistance, acid resistance, and/orother chemical resistance. In a further aspect, a structural supportcomprises a chloro-polymer, a fluoro-polymer, a chloro-fluoro-polymer, ahydrophilic polymer, a hydrophobic polymer, co-polymers thereof,mixtures thereof, or combinations thereof. In a further aspect, astructural support comprises a co-polymer, a block co-polymer, a linearpolymer, a branched polymer, a cross-linked polymer, a heat-treatedpolymer, a solution processed polymer, co-polymers thereof, mixturesthereof, or combinations thereof. In a further aspect, a structuralsupport comprises polyethylene, low density polyethylene, high densitypolyethylene, polypropylene, polyphenylene sulfide, polyester,polytetrafluoroethylene (PTFE), types of polyamide, polyether etherketone (PEEK), polysulfone, polyvinylidene difluoride (PVDF), poly(4-vinyl pyridine-co-styrene) (PVPCS), polystyrene (PS), polybutadiene,acrylonitrile butadiene styrene (ABS), polyvinyl chloride (PVC),polyvinylidene dichloride, ethylene tetrafluoroethylene polymer (ETFE),poly(chlorotrifluoroethylene) (PCTFE), ethylene chlorotrifluoro ethylene(Halar), polyvinylfluoride (PVF), fluorinated ethylene-propylene (FEP),perfluorinated elastomer, chlorotrifluoroethylenevinylidene fluoride(FKM), perfluoropolyether (PFPE), perfluorosulfonic acid (Nafion),polyethylene oxide, polyethylene glycol, sodium polyacrylate,polyethylene-block-poly(ethylene glycol), polyacrylonitrile (PAN),polychloroprene (neoprene), polyvinyl butyral (PVB), expandedpolystyrene (EPS), polydivinylbenzene, co-polymers thereof, mixturesthereof, or combinations thereof. In a further aspect, a structuralsupport comprises polyvinylidene difluoride (PVDF), polyvinyl chloride(PVC), ethylene chlorotrifluoro ethylene (Halar), poly (4-vinylpyridine-co-styrene) (PVPCS), polystyrene (PS), acrylonitrile butadienestyrene (ABS), expanded polystyrene (EPS), polyphenylene sulfide,sulfonated polymer, carboxylated polymer, other polymers, co-polymersthereof, mixtures thereof, or combinations thereof. In a further aspect,a structural support is processed by dry mixing, mixing in solvent,emulsion, extrusion, bubbling one solvent into another, casting,heating, evaporating, vacuum evaporation, spray drying, vapordeposition, chemical vapor deposition, microwaving, hydrothermalsynthesis, polymerization, co-polymerization, cross-linking,irradiation, catalysis, foaming, other deposition methods, orcombinations thereof. In a further aspect, a structural support isdeposited using a solvent comprising n-methyl-2-pyrrolidone, dimethylsulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methylethyl ketone, ethanol, acetone, other solvents, or combinations thereof.

In some embodiments, the porous bead is formed by mixing the ionexchange particles, the matrix material, and the filler materialtogether at once. In one embodiment, the porous bead is formed by firstmixing the ion exchange particles and the matrix material, and thenmixing with the filler material. In some embodiments, the porous bead isformed by first mixing the ion exchange particles and the fillermaterial, and then mixing with the matrix material. In some embodiments,the porous bead is formed by first mixing the matrix material and thefiller material, and then mixing with the ion exchange particles.

In some embodiments, the porous bead is formed by mixing the ionexchange particles, the matrix material, and/or the filler material witha solvent that dissolves once or more of the components. In someembodiments, the filler is a solvent or solution that suspends ordissolves the ion exchange material or matrix material. In someembodiments, the porous bead is formed by mixing the ion exchangeparticles, the matrix material, and/or the filler material as drypowders in a mixer or ball mill. In some embodiments, the porous bead isformed by mixing the ion exchange particles, the matrix material, and/orthe filler material in a spray drier.

In some embodiments, the matrix material is a polymer that is dissolvedand mixed with the ion exchange particles and/or filler material. Insome embodiments, the matrix material is a polymer that is dissolved andmixed with the ion exchange particles and/or filler material using asolvent from the following list: n-methyl-2-pyrrolidone, dimethylsulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methylethyl ketone, ethanol, acetone, other solvents or combinations thereof.In some embodiments, the filler material is a salt that is dissolved andmixed with the ion exchange particles and/or matrix material using asolvent from the following list: water, ethanol, iso-propyl alcohol,acetone, or combinations thereof.

In some embodiments, the filler material is a salt that is dissolved outof the bead to form pores using a solution. In some embodiments, thefiller material is a salt that is dissolved out of the bead to formpores using a solution selected from the following list: water, ethanol,iso-propyl alcohol, a surfactant mixture, an acid, a base, orcombinations thereof. In some embodiments, the filler material is amaterial that thermally decomposes to form a gas at high temperature sothat the gas can leave the bead to form pores. In some embodiments, thefiller material is a material that thermally decomposes to form a gas athigh temperature so that the gas can leave the bead to form pores, wherethe gas is selected from the following list: water vapor, oxygen,nitrogen, chlorine, carbon dioxide, nitrogen oxides, organic vapors, orcombinations thereof.

In some embodiments, the porous ion exchange bead is formed from drypowder. In some embodiments, the porous ion exchange bead is formed fromdry powder using a mechanical press, a pellet press, a tablet press, apill press, a rotary press, dry powder mixing, or combinations thereof.In some embodiments, the porous ion exchange bead is formed from asolvent slurry by dripping, bubbling, or extruding the slurry into adifferent liquid solution. The solvent slurry may be formed using asolvent of n-methyl-2-pyrrolidone, dimethyl sulfoxide, tetrahydrofuran,dimethylformamide, dimethylacetamide, methyl ethyl ketone, orcombinations thereof. The different liquid solution may be formed usingwater, ethanol, iso-propyl alcohol, acetone, or combinations thereof.

In some embodiments, the porous bead is formed by first forming a bulkcomposite and then dividing the bulk composite into smaller beads. Insome embodiments, the beads may be granules. In some embodiments, thebeads may be formed from a bulk composite by slicing, crushing, orgrinding a bulk composite.

An aspect described herein is a porous ion exchange bead comprising ionexchange material and a matrix material, wherein the porous ion exchangebead is prepared by a process comprising the steps of: combining the ionexchange material and the matrix material with a filler material toproduce a precursor bead; and removing the filler material.

In some embodiments, the ion exchange material is selected from coatedion exchange particles, uncoated ion exchange particles, andcombinations thereof.

In some embodiments, the coated ion exchange particles comprise an ionexchange material and a coating material. In some embodiments, thecoating material of the coated ion exchange particles comprises acarbide, a nitride, an oxide, a phosphate, a fluoride, a polymer,carbon, a carbonaceous material, or combinations thereof. In someembodiments, the coating material of the coated ion exchange particlesis selected from the group consisting of TiO₂, ZrO₂, MoO₂, SnO₂, Nb₂O₅,Ta₂O₅, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂SiO₃, Li₂MnO₃, Li₂MoO₃, LiNbO₃,LiTaO₃, AlPO₄, LaPO₄, ZrP₂O₇, MoP₂O₇, MO₂P₃O₁₂, BaSO₄, AlF₃, SiC, TiC,ZrC, Si₃N₄, ZrN, BN, carbon, graphitic carbon, amorphous carbon, hardcarbon, diamond-like carbon, solid solutions thereof, and combinationsthereof. In some embodiments, the coating material of the coated ionexchange particles is selected from the group consisting of TiO₂, ZrO₂,MoO₂, SnO₂, Nb₂O₅, Ta₂O₅, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂SiO₃, Li₂MnO₃,Li₂MoO₃, LiNbO₃, LiTaO₃, AlPO₄, LaPO₄, ZrP₂O₇, MOP₂O₇, MO₂P₃O₁₂, BaSO₄,AlF₃, SiC, TiC, ZrC, Si₃N₄, ZrN, BN, solid solutions thereof, andcombinations thereof. In some embodiments, the coating material is SiO₂or ZrO₂. In some embodiments, the coating material of the coated ionexchange particles is selected from the group consisting of carbon,graphitic carbon, amorphous carbon, hard carbon, diamond-like carbon,solid solutions thereof, and combinations thereof. In some embodiments,the coating material of the coated ion exchange particles is selectedfrom the group consisting of polyvinyl fluoride, polyvinylidenedifluoride, polyvinyl chloride, polyvinylidene dichloride, polyethylene,polypropylene, polyphenylene sulfide, polytetrafluoroethylene,polytetrofluoroethylene, sulfonated polytetrofluoroethylene,polystyrene, polydivinylbenzene, polybutadiene,poly-ethylene-tetrafluoroethyelene, polyacrylonitrile, sulfonatedpolymer, carboxylated polymer,tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer, copolymers thereof, and combinations thereof.

In some of embodiments, the ion exchange material of the coated ionexchange particles comprises an oxide, a phosphate, an oxyfluoride, afluorophosphate, or combinations thereof. In some embodiments, the ionexchange material of the coated ion exchange particles is selected fromthe group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂, Li₂TiO₃, Li₂MnO₃, Li₂SnO₃,LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂, LiTiO₂, Li₄TiO₄,Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄, Li₂CuP₂O₇, Al(OH)₃,LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O, TiO₂.xSb₂O₅.yH₂O, solid solutionsthereof, and combinations thereof, wherein x is from 0.1-10; and y isfrom 0.1-10. In some embodiments, x is selected from 0.1, 0.2, 0.3, 0.4,0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. In someembodiments, y is selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8,0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. In some embodiments, x and y areindependently selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9,1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. In some embodiments, the ion exchangematerial of the coated ion exchange particles is selected from Li₂SnO₃,Li₂MnO₃, Li₂TiO₃, Li₄Ti₅O₁₂, Li₄Mn₅O₁₂, Li_(1.6)Mn_(1.6)O₄, andcombinations thereof. In some embodiments, the ion exchange material ofthe coated ion exchange particles is Li₄Mn₅O₁₂.

In some embodiments, the uncoated ion exchange particles comprise an ionexchange material. In some embodiments, the ion exchange material of theuncoated ion exchange particles comprises an oxide, a phosphate, anoxyfluoride, a fluorophosphate, or combinations thereof. In someembodiments, the ion exchange material of the uncoated ion exchangeparticles is selected from the group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂,Li₂TiO₃, Li₂MnO₃, Li₂SnO₃, LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂,LiTiO₂, Li₄TiO₄, Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄,Li₂CuP₂O₇, Al(OH)₃, LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O,TiO₂.xSb₂O₅.yH₂O, solid solutions thereof, and combinations thereof;wherein x is from 0.1-10; and y is from 0.1-10. In some embodiments, xis selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3,4, 5, 6, 7, 8, 9, and 10. In some embodiments, y is selected from 0.1,0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and10. In some embodiments, x and y are independently selected from 0.1,0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and10. In some embodiments, the ion exchange material of the uncoated ionexchange particles is selected from Li₂SnO₃, Li₂MnO₃, Li₂TiO₃,Li₄Ti₅O₁₂, Li₄Mn₅O₁₂, Li_(1.6)Mn_(1.6)O₄, and combinations thereof. Insome embodiments, the ion exchange material of the uncoated ion exchangeparticles is Li₄Mn₅O₁₂.

In some embodiments, the matrix material comprises a polymer, an oxide,a phosphate, or combinations thereof. In some embodiments, the matrixmaterial is selected from the group consisting of polyvinyl fluoride,polyvinylidene difluoride, polyvinyl chloride, polyvinylidenedichloride, polyethylene, polypropylene, polyphenylene sulfide,polytetrafluoroethylene, polytetrofluoroethylene, sulfonatedpolytetrofluoroethylene, polystyrene, polydivinylbenzene, polybutadiene,poly-ethylene-tetrafluoroethyelene, polyacrylonitrile, sulfonatedpolymer, carboxylated polymer,tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer, copolymers thereof, and combinations thereof.

In some embodiments, the filler material is removed by treating theprecursor bead with a solvent. In some embodiments, the solventdissolves the filler material in the precursor bead. In someembodiments, the solvent is selected from the group consisting of water,ethanol, iso-propyl alcohol, acetone, and combinations thereof.

In some embodiments, the filler material comprises a salt, a liquid, anorganic material, or a combination of one or more thereof. In someembodiments, the filler material is a salt. In some embodiments, thefiller material is a halide salt, a sulfate salt, a bisulfate salt, acarbonate salt, a bicarbonate salt, a nitrate salt, an alkali metalsalt, an alkali earth metal salt, or combinations of one or morethereof. In some embodiments the halide salt is a chloride salt, abromide salt, a fluoride salt, an iodide salt, or combinations thereof.In some embodiments, the filler material is an organic material. In someembodiments, the filler material is an organic material, wherein theorganic material is a polymer or an organic liquid. In some embodiments,the filler material is a liquid. In some embodiments, the fillermaterial is a liquid, wherein the liquid is an organic liquid, anaqueous liquid, or combinations thereof. In some embodiments, the fillermaterial is a chloride salt, sodium chloride, a sulfate salt, acarbonate salt, a nitrate salt, an alkali metal salt, an alkali earthmetal salt, an organic material, a polymer, an aqueous liquid, anorganic liquid, a liquid mixture, or combinations thereof. In someembodiments, the filler material is sodium chloride.

In some embodiments, the filler material is removed by sublimation orevaporation, optionally subjecting the precursor bead to heat, vacuum,air, or combinations thereof. In some embodiments, the filler materialis removed by sublimation or evaporation, optionally subjecting theprecursor bead to heat, sub-atmospheric pressure, ambient air, orcombinations thereof. In some embodiments, the filler material isremoved by subjecting the precursor bead to heat. In some embodiments,the heat decomposes the filler material. In some embodiments, the heatdecomposes a portion or essentially all of the filler material. In someembodiments, the heat decomposes a portion of the filler material. Insome embodiments, the heat decomposes essentially all of the fillermaterial. In some embodiments, the filler comprises a solvent that maydissolve or suspend the ion exchange material or the matrix material. Insome embodiments, the filler comprises a surfactant that may dissolve orsuspend the ion exchange material or the matrix material.

In some embodiments, the porous ion exchange bead is approximatelyspherical with an average diameter selected from the following list:less than 10 um, less than 100 um, less than 1 mm, less than 1 cm, orless than 10 cm. In some embodiments, the porous ion exchange bead isapproximately spherical with an average diameter selected from thefollowing list: less than 200 um, less than 2 mm, or less than 20 mm. Insome embodiments, the porous ion exchange bead is non-spherical,irregularly shaped, or granular.

In some embodiments, the porous ion exchange beads have a number averagediameter less than about 10 μm. In some embodiments, the porous ionexchange beads have a number average diameter less than about 100 μm. Insome embodiments, the porous ion exchange beads have a number averagediameter less than about 1,000 μm. In some embodiments, the porous ionexchange beads have a number average diameter greater than about 1,000μm. In some embodiments, the porous ion exchange beads have a weightaverage diameter less than about 10 μm. In some embodiments, the porousion exchange beads have a weight average diameter less than about 100μm. In some embodiments, the porous ion exchange beads have a weightaverage diameter less than about 1,000 μm. In some embodiments, theporous ion exchange beads have a weight average diameter greater thanabout 1,000 μm.

In some embodiments, the porous ion exchange bead has an averagediameter of less than about 10 μm, less than about 20 μm, less thanabout 30 μm, less than about 40 μm, less than about 50 μm, less thanabout 60 μm, less than about 70 μm, less than about 80 μm, less thanabout 90 μm, less than about 100 μm, less than about 1,000 μm, less thanabout 10,000 μm, less than about 100,000 μm, more than about 10 μm, morethan about 20 μm, more than about 30 μm, more than about 40 μm, morethan about 50 μm, more than about 60 μm, more than about 70 μm, morethan about 80 μm, more than about 90 μm, more than about 100 μm, morethan about 1,000 μm, more than about 10,000 μm, from about 1 μm to about10,000 μm, from about 1 μm to about 1,000 μm, from about 1 μm to about100 μm, from about 1 μm to about 80 μm, from about 1 μm to about 60 μm,from about 1 μm to about 40 μm, or from about 1 μm to about 20 μm. Insome embodiments, the porous ion exchange bead has an average size ofless than about 100 μm, less than about 1,000 μm, or less than about10,000 μm. In some embodiments, the porous ion exchange bead has anaverage diameter from about 1 μm to about 300 μm, from about 1 μm toabout 200 μm, from about 1 μm to about 100 μm, from about 1 μm to about80 μm, from about 1 μm to about 60 μm, from about 1 μm to about 40 μm,or from about 1 μm to about 20 μm. In some embodiments, the porous ionexchange bead is tablet-shaped with a diameter of less than 1 mm, lessthan 2 mm, less than 4 mm, less than 8 mm, or less than 20 mm and with aheight of less than 1 mm, less than 2 mm, less than 4 mm, less than 8mm, or less than 20 mm. In some embodiments, the porous ion exchangebead has an irregular shape or granule shape. In some embodiments, theporous ion exchange bead is processed with crushing, slicing, grinding,or combinations thereof.

In some embodiments, the porous ion exchange bead is embedded in asupport structure, which may be a membrane, a spiral-wound membrane, ahollow fiber membrane, or a mesh. In some embodiments, the porous ionexchange bead is embedded on a support structure comprised of a polymer,a ceramic, or combinations thereof. In some embodiments, the porous ionexchange bead is loaded directly into an ion exchange vessel with noadditional support structure. In some embodiments, the porous ionexchange bead is loaded into a compartment, a stirred tank reactor, or acompartment in a stirred tank reactor.

An aspect described herein is a method of making porous ion exchangebeads, comprising: (a) combining and mixing ion exchange particles thatreversibly exchange lithium and hydrogen, a matrix material, and afiller material to make a mixture; (b) forming the mixture into beads;(c) optionally heating the beads; and (d) removing a portion oressentially all of the filler material to make porous ion exchangebeads.

In some embodiments, the combining and mixing are done using drypowders. In some embodiments, the combining and mixing are done usingone or more solvents and the mixture is a slurry. In some embodiments,the forming is done using a mechanical press. In some embodiments, theforming is done by injecting the slurry into a liquid. In someembodiments, the heating is sufficient to melt or sinter the matrixmaterial.

In some embodiments, the removing is done by dissolving the fillermaterial using a solvent. In some embodiments, the removing is done bydissolving the filler material using a solvent wherein the solvent is anaqueous solvent, an organic solvent, or a mixture of one or more aqueoussolvents and one or more organic solvents. In some embodiments, theremoving is done by dissolving the filler material using an aqueoussolvent comprising an acid, a base, a brine, or a combination thereof.In some embodiments, the removing is done by dissolving the fillermaterial using water. In some embodiments, the removing is done bydissolving the filler material using a brine. In some embodiments, theremoving is done by dissolving the filler material using an organicsolvent. In some embodiments, the removing is done by dissolving thefiller material using an organic solvent, wherein the organic solvent isan alcohol, a ketone, an aldehyde, an amine, a carboxylic acid, or acombination thereof. In some embodiments, the removing is done bydissolving the filler material using an alcohol. In some embodiments,the removing is done by dissolving the filler material using an alcohol,wherein the alcohol is methanol, ethanol, normal-propanol, isopropanol,normal-butanol, isobutanol, tertiary-butanol, or combinations thereof.In some embodiments, the removing is done by dissolving the fillermaterial using a ketone, wherein the ketone is acetone,methylethylketone, or combinations thereof. In some embodiments, theremoving is done by dissolving the filler material using acetone. Insome embodiments, the removing is done by dissolving the filler materialusing a mixture of water and acetone. In some embodiments, the removingis done by dissolving the filler material using water, an aqueoussolution, an acid, a brine, an alcohol, or combinations thereof. In someembodiments, the removing is done by dissolving the filler materialusing an aqueous solution, an alcohol, or combinations thereof.

In some embodiments, the removing is done by heating the beads. In someembodiments, the removing is done by heating the beads to decompose thefiller material. In some embodiments, the removing is done by heatingthe beads sufficient to decompose the filler material to gaseousparticles or decomposition products. In some embodiments, the removingis done by heating the beads to decompose the filler material tovolatile decomposition products. In some embodiments, the removing isdone by heating the beads to evaporate the filler material. In someembodiments, the removing is done by heating the beads to evaporate thefiller material and then the filler material is captured and reused.

An aspect described herein is a method of making a porous ion exchangebead for extraction of lithium from a liquid resource comprising:forming a precursor bead wherein the precursor bead comprises an ionexchange material, a matrix material and a filler material; and removingat least a portion of the filler material to produce the porous ionexchange bead.

In some embodiments, the removing is done by putting the precursor beadinto service intended for the porous ion exchange bead and by dissolvingthe filler material using the service medium as a solvent.

In some embodiments, essentially all of the filler material is removed.In some embodiments, a portion of the filler material is removed.

In some embodiments, the ion exchange material is selected from coatedion exchange particles, uncoated ion exchange particles, andcombinations thereof.

In some embodiments, the coated ion exchange particles comprise an ionexchange material and a coating material. In some embodiments, thecoating material of the coated ion exchange particles comprises acarbide, a nitride, an oxide, a phosphate, a fluoride, a polymer,carbon, a carbonaceous material, or combinations thereof. In someembodiments, the coating material of the coated ion exchange particlesis selected from the group consisting of TiO₂, ZrO₂, MoO₂, SnO₂, Nb₂O₅,Ta₂O₅, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂SiO₃, Li₂MnO₃, Li₂MoO₃, LiNbO₃,LiTaO₃, AlPO₄, LaPO₄, ZrP₂O₇, MoP₂O₇, MO₂P₃O₁₂, BaSO₄, AlF₃, SiC, TiC,ZrC, Si₃N₄, ZrN, BN, carbon, graphitic carbon, amorphous carbon, hardcarbon, diamond-like carbon, solid solutions thereof, and combinationsthereof. In some embodiments, the coating material of the coated ionexchange particles is selected from the group consisting of TiO₂, ZrO₂,MoO₂, SnO₂, Nb₂O₅, Ta₂O₅, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂SiO₃, Li₂MnO₃,Li₂MoO₃, LiNbO₃, LiTaO₃, AlPO₄, LaPO₄, ZrP₂O₇, MOP₂O₇, MO₂P₃O₁₂, BaSO₄,AlF₃, SiC, TiC, ZrC, Si₃N₄, ZrN, BN, solid solutions thereof, andcombinations thereof. In some embodiments, the coating material is SiO₂or ZrO₂. In some embodiments, the coating material of the coated ionexchange particles is selected from the group consisting of carbon,graphitic carbon, amorphous carbon, hard carbon, diamond-like carbon,solid solutions thereof, and combinations thereof. In some embodiments,the coating material of the coated ion exchange particles is selectedfrom the group consisting of polyvinyl fluoride, polyvinylidenedifluoride, polyvinyl chloride, polyvinylidene dichloride, polyethylene,polypropylene, polyphenylene sulfide, polytetrafluoroethylene,polytetrofluoroethylene, sulfonated polytetrofluoroethylene,polystyrene, polydivinylbenzene, polybutadiene,poly-ethylene-tetrafluoroethyelene, polyacrylonitrile, sulfonatedpolymer, carboxylated polymer,tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer, copolymers thereof, and combinations thereof.

In some of embodiments, the ion exchange material of the coated ionexchange particles comprises an oxide, a phosphate, an oxyfluoride, afluorophosphate, or combinations thereof. In some embodiments, the ionexchange material of the coated ion exchange particles is selected fromthe group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂, Li₂TiO₃, Li₂MnO₃, Li₂SnO₃,LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂, LiTiO₂, Li₄TiO₄, Li₇Ti₁O₂₄,Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄, Li₂CuP₂O₇, Al(OH)₃,LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O, TiO₂.xSb₂O₅.yH₂O, solid solutionsthereof, and combinations thereof, wherein x is from 0.1-10; and y isfrom 0.1-10. In some embodiments, x is selected from 0.1, 0.2, 0.3, 0.4,0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. In someembodiments, y is selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8,0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. In some embodiments, x and y areindependently selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9,1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. In some embodiments, the ion exchangematerial of the coated ion exchange particles is selected from Li₂SnO₃,Li₂MnO₃, Li₂TiO₃, Li₄Ti₅O₁₂, Li₄Mn₅O₁₂, Li_(1.6)Mn_(1.6)O₄, andcombinations thereof. In some embodiments, the ion exchange material ofthe coated ion exchange particles is Li₄Mn₅O₁₂.

In some embodiments, the uncoated ion exchange particles comprise an ionexchange material. In some embodiments, the ion exchange material of theuncoated ion exchange particles comprises an oxide, a phosphate, anoxyfluoride, a fluorophosphate, or combinations thereof. In someembodiments, the ion exchange material of the uncoated ion exchangeparticles is selected from the group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂,Li₂TiO₃, Li₂MnO₃, Li₂SnO₃, LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂,LiTiO₂, Li₄TiO₄, Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄,Li₂CuP₂O₇, Al(OH)₃, LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O,TiO₂.xSb₂O₅.yH₂O, solid solutions thereof, and combinations thereof,wherein x is from 0.1-10; and y is from 0.1-10. In some embodiments, xis selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3,4, 5, 6, 7, 8, 9, and 10. In some embodiments, y is selected from 0.1,0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and10. In some embodiments, x and y are independently selected from 0.1,0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and10. In some embodiments, the ion exchange material of the uncoated ionexchange particles is selected from Li₂SnO₃, Li₂MnO₃, Li₂TiO₃,Li₄Ti₅O₁₂, Li₄Mn₅O₁₂, Li_(1.6)Mn_(1.6)O₄, and combinations thereof. Insome embodiments, the ion exchange material of the uncoated ion exchangeparticle is Li₄Mn₅O₁₂.

In some embodiments, the matrix material comprises a polymer, an oxide,a phosphate, or combinations thereof. In some embodiments, the matrixmaterial is selected from the group consisting of polyvinyl fluoride,polyvinylidene difluoride, polyvinyl chloride, polyvinylidenedichloride, polyethylene, polypropylene, polyphenylene sulfide,polytetrafluoroethylene, polytetrofluoroethylene, sulfonatedpolytetrofluoroethylene, polystyrene, polydivinylbenzene, polybutadiene,poly-ethylene-tetrafluoroethyelene, polyacrylonitrile, sulfonatedpolymer, carboxylated polymer,tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer, copolymers thereof, and combinations thereof.

In some embodiments, the filler material is removed by treating theprecursor bead with a solvent. In some embodiments, the solventdissolves the filler material in the precursor bead. In someembodiments, the solvent is selected from the group consisting of water,ethanol, iso-propyl alcohol, acetone, and combinations thereof.

In some embodiments, the filler material comprises a salt, a liquid, anorganic material, or a combination of one or more thereof. In someembodiments, the filler material is a salt. In some embodiments, thefiller material is a halide salt, a sulfate salt, a bisulfate salt, acarbonate salt, a bicarbonate salt, a nitrate salt, an alkali metalsalt, an alkali earth metal salt, or combinations of one or morethereof. In some embodiments the halide salt is a chloride salt, abromide salt, a fluoride salt, an iodide salt, or combinations thereof.In some embodiments, the filler material is an organic material. In someembodiments, the filler material is an organic material, wherein theorganic material is a polymer or an organic liquid. In some embodiments,the filler material is a liquid. In some embodiments, the fillermaterial is a liquid, wherein the liquid is an organic liquid, anaqueous liquid, or combinations thereof. In some embodiments, the fillermaterial is a chloride salt, sodium chloride, a sulfate salt, acarbonate salt, a nitrate salt, an alkali metal salt, an alkali earthmetal salt, an organic material, a polymer, an aqueous liquid, anorganic liquid, a liquid mixture, or combinations thereof. In someembodiments, the filler material is sodium chloride.

In some embodiments, the filler material is removed by sublimation orevaporation, optionally subjecting the precursor bead to heat, vacuum,air, or combinations thereof. In some embodiments, the filler materialis removed by sublimation or evaporation, optionally subjecting theprecursor bead to heat, sub-atmospheric pressure, ambient air, orcombinations thereof. In some embodiments, the filler material isremoved by subjecting the precursor bead to heat. In some embodiments,the heat decomposes the filler material. In some embodiments, the heatdecomposes a portion or essentially all of the filler material. In someembodiments, the heat decomposes a portion of the filler material. Insome embodiments, the heat decomposes essentially all of the fillermaterial.

An aspect described herein is a method of making porous ion exchangebeads, comprising: (a) combining and mixing ion exchange particles thatreversibly exchange lithium and hydrogen, a matrix material, and afiller material to make a mixture; (b) forming the mixture into beads;(c) optionally heating the beads; and (d) removing a portion oressentially all of the filler material to make porous ion exchangebeads, wherein the ion exchange material is selected from coated ionexchange particles, uncoated ion exchange particles, and combinationsthereof.

In some embodiments, the coated ion exchange particles comprise an ionexchange material and a coating material. In some embodiments, thecoating material of the coated ion exchange particles comprises acarbide, a nitride, an oxide, a phosphate, a fluoride, a polymer,carbon, a carbonaceous material, or combinations thereof. In someembodiments, the coating material of the coated ion exchange particlesis selected from the group consisting of TiO₂, ZrO₂, MoO₂, SnO₂, Nb₂O₅,Ta₂O₅, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂SiO₃, Li₂MnO₃, Li₂MoO₃, LiNbO₃,LiTaO₃, AlPO₄, LaPO₄, ZrP₂O₇, MoP₂O₇, MO₂P₃O₁₂, BaSO₄, AlF₃, SiC, TiC,ZrC, Si₃N₄, ZrN, BN, carbon, graphitic carbon, amorphous carbon, hardcarbon, diamond-like carbon, solid solutions thereof, and combinationsthereof. In some embodiments, the coating material of the coated ionexchange particles is selected from the group consisting of TiO₂, ZrO₂,MoO₂, SnO₂, Nb₂O₅, Ta₂O₅, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂SiO₃, Li₂MnO₃,Li₂MoO₃, LiNbO₃, LiTaO₃, AlPO₄, LaPO₄, ZrP₂O₇, MOP₂O₇, MO₂P₃O₁₂, BaSO₄,AlF₃, SiC, TiC, ZrC, Si₃N₄, ZrN, BN, solid solutions thereof, andcombinations thereof. In some embodiments, the coating material is SiO₂or ZrO₂. In some embodiments, the coating material of the coated ionexchange particles is selected from the group consisting of carbon,graphitic carbon, amorphous carbon, hard carbon, diamond-like carbon,solid solutions thereof, and combinations thereof. In some embodiments,the coating material of the coated ion exchange particles is selectedfrom the group consisting of polyvinyl fluoride, polyvinylidenedifluoride, polyvinyl chloride, polyvinylidene dichloride, polyethylene,polypropylene, polyphenylene sulfide, polytetrafluoroethylene,polytetrofluoroethylene, sulfonated polytetrofluoroethylene,polystyrene, polydivinylbenzene, polybutadiene,poly-ethylene-tetrafluoroethyelene, polyacrylonitrile, sulfonatedpolymer, carboxylated polymer,tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer, copolymers thereof, and combinations thereof.

In some of embodiments, the ion exchange material of the coated ionexchange particles comprises an oxide, a phosphate, an oxyfluoride, afluorophosphate, or combinations thereof. In some embodiments, the ionexchange material of the coated ion exchange particles is selected fromthe group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂, Li₂TiO₃, Li₂MnO₃, Li₂SnO₃,LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂, LiTiO₂, Li₄TiO₄,Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄, Li₂CuP₂O₇, Al(OH)₃,LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O, TiO₂.xSb₂O₅.yH₂O, solid solutionsthereof, and combinations thereof, wherein x is from 0.1-10; and y isfrom 0.1-10. In some embodiments, x is selected from 0.1, 0.2, 0.3, 0.4,0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. In someembodiments, y is selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8,0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. In some embodiments, x and y areindependently selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9,1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. In some embodiments, the ion exchangematerial of the coated ion exchange particles is selected from Li₂SnO₃,Li₂MnO₃, Li₂TiO₃, Li₄Ti₅O₁₂, Li₄Mn₅O₁₂, Li_(1.6)Mn_(1.6)O₄, andcombinations thereof. In some embodiments, the ion exchange material ofthe coated ion exchange particles is Li₄Mn₅O₁₂.

In some embodiments, the uncoated ion exchange particles comprise an ionexchange material. In some embodiments, the ion exchange material of theuncoated ion exchange particles comprises an oxide, a phosphate, anoxyfluoride, a fluorophosphate, or combinations thereof. In someembodiments, the ion exchange material of the uncoated ion exchangeparticles is selected from the group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂,Li₂TiO₃, Li₂MnO₃, Li₂SnO₃, LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂,LiTiO₂, Li₄TiO₄, Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄,Li₂CuP₂O₇, Al(OH)₃, LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O,TiO₂.xSb₂O₅.yH₂O, solid solutions thereof, and combinations thereof,wherein x is from 0.1-10; and y is from 0.1-10. In some embodiments, xis selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3,4, 5, 6, 7, 8, 9, and 10. In some embodiments, y is selected from 0.1,0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and10. In some embodiments, x and y are independently selected from 0.1,0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and10. In some embodiments, the ion exchange material of the uncoated ionexchange particles is selected from Li₂SnO₃, Li₂MnO₃, Li₂TiO₃,Li₄Ti₅O₁₂, Li₄Mn₅O₁₂, Li_(1.6)Mn_(1.6)O₄, and combinations thereof. Insome embodiments, the ion exchange material of the uncoated ion exchangeparticles is Li₄Mn₅O₁₂.

In some embodiments, the matrix material comprises a polymer, an oxide,a phosphate, or combinations thereof. In some embodiments, the matrixmaterial is selected from the group consisting of polyvinyl fluoride,polyvinylidene difluoride, polyvinyl chloride, polyvinylidenedichloride, polyethylene, polypropylene, polyphenylene sulfide,polytetrafluoroethylene, polytetrofluoroethylene, sulfonatedpolytetrofluoroethylene, polystyrene, polydivinylbenzene, polybutadiene,poly-ethylene-tetrafluoroethyelene, polyacrylonitrile, sulfonatedpolymer, carboxylated polymer,tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer, copolymers thereof, and combinations thereof.

In some embodiments, the filler material comprises a salt, a liquid, anorganic material, or a combination of one or more thereof. In someembodiments, the filler material is a salt. In some embodiments, thefiller material is a halide salt, a sulfate salt, a bisulfate salt, acarbonate salt, a bicarbonate salt, a nitrate salt, an alkali metalsalt, an alkali earth metal salt, or combinations of one or morethereof. In some embodiments the halide salt is a chloride salt, abromide salt, a fluoride salt, an iodide salt, or combinations thereof.In some embodiments, the filler material is an organic material. In someembodiments, the filler material is an organic material, wherein theorganic material is a polymer or an organic liquid. In some embodiments,the filler material is a liquid. In some embodiments, the fillermaterial is a liquid, wherein the liquid is an organic liquid, anaqueous liquid, or combinations thereof. In some embodiments, the fillermaterial is a chloride salt, sodium chloride, a sulfate salt, acarbonate salt, a nitrate salt, an alkali metal salt, an alkali earthmetal salt, an organic material, a polymer, an aqueous liquid, anorganic liquid, a liquid mixture, or combinations thereof. In someembodiments, the filler material is sodium chloride.

In some embodiments, the liquid resource is selected from the followinglist: a natural brine, a dissolved salt flat, a geothermal brine,seawater, concentrated seawater, desalination effluent, a concentratedbrine, a processed brine, liquid from an ion exchange process, liquidfrom a solvent extraction process, a synthetic brine, leachate fromores, leachate from minerals, leachate from clays, leachate fromrecycled products, leachate from recycled materials, or combinationsthereof. In some embodiments, a liquid resource is selected from thefollowing list: a natural brine, a dissolved salt flat, a concentratedbrine, a processed brine, a synthetic brine, a geothermal brine, liquidfrom an ion exchange process, liquid from a solvent extraction process,leachate from minerals, leachate from clays, leachate from recycledproducts, leachate from recycled materials, or combinations thereof.

In some embodiments, the liquid resource is selected with a lithiumconcentration selected from the following list: less than 100,000 ppm,less than 10,000 ppm, less than 1,000 ppm, less than 100 ppm, less than10 ppm, or combinations thereof. In some embodiments, a liquid resourceis selected with a lithium concentration selected from the followinglist: less than 5,000 ppm, less than 500 ppm, less than 50 ppm, orcombinations thereof.

In some embodiments, the acid used for recovering lithium from theporous ion exchange beads is selected from the following list:hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid,chloric acid, perchloric acid, nitric acid, formic acid, acetic acid, orcombinations thereof. In some embodiments, the acid used for recoveringlithium from the porous ion exchange beads is selected from thefollowing list: hydrochloric acid, sulfuric acid, nitric acid, orcombinations thereof.

In some embodiments, the acid used for recovering lithium from theporous ion exchange beads has a concentration selected from thefollowing list: less than 0.1 M, less than 1.0 M, less than 5 M, lessthan 10 M, or combinations thereof. In some embodiments, lithium may berecovered from the porous ion exchange beads by exposing the beads toone acid and then exposing the beads to a second acid. In someembodiments, lithium may be recovered from the porous ion exchange beadsby first adding an acid of a lower concentration or water, and thenadding a more concentrated acid.

In some embodiments, the porous ion exchange beads perform the ionexchange reaction repeatedly over a number of cycles selected from thefollowing list: greater than 10 cycles, greater than 30 cycles, greaterthan 100 cycles, greater than 300 cycles, greater than 1,000 cycles, orgreater than 5,000 cycles. In some embodiments, the porous ion exchangebeads perform the ion exchange reaction repeatedly over a number ofcycles selected from the following list: greater than 100 cycles,greater than 300 cycles, or greater than 1,000 cycles.

In some embodiments, the concentrated lithium solution that is yieldedfrom the porous ion exchange beads is further processed into lithium rawmaterials using methods selected from the following list: solventextraction, ion exchange, chemical precipitation, electrolysis,electrodialysis, electrowinning, evaporation with direct solar energy,evaporation with concentrated solar energy, evaporation with a heattransfer medium heated by concentrated solar energy, evaporation withheat from a geothermal brine, evaporation with heat from combustion,reverse osmosis, nano-filtration, or combinations thereof.

In some embodiments, the concentrated lithium solution that is yieldedfrom the porous ion exchange beads is further processed into lithiumchemicals selected from the following list: lithium chloride, lithiumcarbonate, lithium hydroxide, lithium metal, lithium metal oxide,lithium metal phosphate, lithium sulfide, lithium sulfate, lithiumphosphate, or combinations thereof. In some embodiments, theconcentrated lithium solution that is yielded from the porous ionexchange beads is further processed into lithium chemicals that aresolid, liquid, hydrated, or anhydrous.

In some embodiments, the lithium chemicals produced using the porous ionexchange beads are used in an industrial application selected from thefollowing list: lithium batteries, metal alloys, glass, grease, orcombinations thereof. In some embodiments, the lithium chemicalsproduced using the coated ion exchange particles are used in anapplication selected from the following list: lithium batteries,lithium-ion batteries, lithium sulfur batteries, lithium solid-statebatteries, and combinations thereof.

In some embodiments, the ion exchange materials are synthesized in alithiated state with a sublattice fully or partly occupied by lithium.In some embodiments, the ion exchange materials are synthesized in ahydrated state with a sublattice fully or partly occupied by hydrogen.

An aspect described herein is a method of extracting lithium from aliquid resource, comprising: (a) contacting a porous ion exchange beadcomprising ion exchange material and a matrix material, wherein theporous ion exchange bead is prepared by a process comprising the stepsof: (i) combining the ion exchange material and the matrix material witha filler material to produce a precursor bead; and (ii) removing thefiller material, with a liquid resource to produce a lithiated porousion exchange bead; and (b) treating the lithiated porous ion exchangebead with an acid solution to produce a salt solution comprising lithiumions.

In some embodiments of the methods described herein, the liquid resourceis a natural brine, a dissolved salt flat, seawater, concentratedseawater, a desalination effluent, a concentrated brine, a processedbrine, waste brine from a bromine-extraction process, an oilfield brine,a liquid from an ion exchange process, a liquid from a solventextraction process, a synthetic brine, a leachate from an ore orcombination of ores, a leachate from a mineral or combination ofminerals, a leachate from a clay or combination of clays, a leachatefrom recycled products, a leachate from recycled materials, orcombinations thereof. In some embodiments of the methods describedherein, the liquid resource is a brine. In some embodiments of themethods described herein, the liquid resource comprises a natural brine,a synthetic brine, or a mixture of a natural and a synthetic brine. Insome embodiments of the methods described herein, the liquid resource isa natural brine, a dissolved salt flat, seawater, concentrated seawater,a desalination effluent, a concentrated brine, a processed brine, wastebrine from a bromine-extraction process, an oilfield brine, a liquidfrom an ion exchange process, or combinations thereof.

In some embodiments of the methods described herein, the acid solutioncomprises hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromicacid, chloric acid, perchloric acid, nitric acid, formic acid, aceticacid, or combinations thereof. In some embodiments of the methodsdescribed herein, the acid solution comprises hydrochloric acid,sulfuric acid, phosphoric acid, nitric acid, or combinations thereof. Insome embodiments of the methods described herein, the acid solutioncomprises hydrochloric acid, sulfuric acid, phosphoric acid, orcombinations thereof. In some embodiments of the methods describedherein the acid solution comprises hydrochloric acid. In someembodiments of the methods described herein the acid solution comprisessulfuric acid. In some embodiments of the methods described herein theacid solution comprises phosphoric acid.

In some embodiments, the method is conducted in a column, a vessel, or astirred tank reactor. In some embodiments the method is conducted in avessel. In some embodiments the method is conducted in a vessel, whereinthe vessel is a stirred tank or a column. In some embodiments, themethod is conducted in a plurality of vessels. In some embodiments, themethod is conducted in a plurality of vessels that are in fluidcommunication with each other. In some embodiments, one or more of theplurality of vessels is a column and one or more of the plurality ofvessels is a stirred tank.

EXAMPLES Example 1: Porous Ion Exchange Beads with PVC Matrix

Lithium is extracted from a brine using porous ion exchange beads. Thebrine is an aqueous chloride solution containing 100 ppm Li, 40,000 ppmNa, 30,000 ppm Ca, and 3,000 ppm Mg. The porous ion exchange beads arecomprised of ion exchange particles and a polymer matrix. The ionexchange particles are comprised of a Li₄Mn₅O₁₂ core with a ZrO₂coating. The ion exchange particles contain 99 wt % Li₄Mn₅O₁₂ and 1 wt %ZrO₂. The particles are approximately spherical with a mean diameter of1.0 microns, and the coating thickness is approximately 1 nm. Thepolymer matrix is comprised of PVC. The porous beads contain pores witha distribution of pore sizes providing diffusion channels from the beadsurface into the bead interior and to the ion exchange particles. Whenthe porous beads are submerged in aqueous or other solutions, the poresare infiltrated with the solutions. The beads have a distribution ofshapes that are approximately spherical on average with a 1.0 mm averagediameter.

The porous ion exchange beads are created by combining three components:ion exchange particles, a polymer, and a removable filler material. Thefiller material is potassium sulfate. The three components are mixedtogether using a solvent mixture of n-methyl-2-pyrrolidone, ethanol, andwater, and then the solvent is removed. The resulting mixture is groundand formed into beads using a mechanical press. The beads are heated toalter the structure of the polymer and improve mechanical strength. Thefiller is removed using water, which dissolves the filler and therebyleaves behind pores throughout the bead. The bead is heated again toalter the structure of the polymer and further improve mechanicalstrength.

The porous beads are treated with HCl acid to yield LiCl in solution.1.0 g of the beads are stirred in 30 mL of 1.0 M HCl acid for 4 hours atroom temperature. The pores in the beads allow the acid solution topenetrate into the bead and access the ion exchange particles.Therefore, the ion exchange particles can absorb hydrogen from the acidwhile releasing lithium into the acid. The Li₄Mn₅O₁₂ active material isconverted to a hydrogenated state with a hydrogen-rich compositionLi_(4-x)H_(x)Mn₅O₁₂ where x may be close to 4. The ZrO₂ coating allowsdiffusion of hydrogen and lithium respectively to and from the activematerial while providing a protective barrier that limits dissolution ofmanganese and oxygen from the active material. After 4 hours ofstirring, the solution is collected for elemental analysis to measurelithium yield.

After treatment in acid, the hydrogenated beads are treated with brinewherein the particles absorb lithium while releasing hydrogen. Thehydrogenated beads are stirred in 1.0 L of brine for 4 hours at roomtemperature. The pores in the beads allow the brine solution topenetrate into the bead and access the ion exchange particles.Therefore, the ion exchange particles can absorb lithium from the brinewhile releasing hydrogen into the brine. The beads are converted from ahydrogenated state to a lithiated state with a lithium-rich compositionLi_(4-x)H_(x)Mn₅O₁₂ where x may be close to 0. After 4 hours ofstirring, the solution is collected for elemental analysis to measurelithium uptake.

The lithiated beads are then treated again with acid to yield lithium insolution as described previously. The cycle of hydrogenation andlithiation is repeated to extract lithium from the brine and yield aLiCl solution. The pores in the beads facilitate penetration of the acidand brine solutions into the beads, facilitating absorption and releaseof lithium and hydrogen by the ion exchange particle. Dissolution anddegradation of the active material in acid is limited due to the ZrO₂coating providing a protective barrier. Dissolution of the activematerial is measured with elemental analysis of the acid solutionfollowing stirring.

Example 2: Ion Exchange Column with Fixed Bed of Porous Beads

Lithium is extracted from a brine using an ion exchange column loadedwith a fixed bed of porous ion exchange particles. The brine is anatural chloride solution containing approximately 100 ppm Li, 40,000ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg. The porous ion exchange beadsare comprised of ion exchange particles and a polymer matrix. The ionexchange particles are comprised of a Li₄Mn₅O₁₂ core with a ZrO₂coating. The ion exchange particles contain 99 wt % Li₄Mn₅O₁₂ and 1 wt %ZrO₂. The particles are approximately spherical with a mean diameter of1.0 microns, and the coating thickness is approximately 1.0 nm. Thepolymer matrix is comprised of PVC. The porous beads contain pores witha distribution of pore sizes providing diffusion channels from the beadsurface into the bead interior and to the ion exchange particles. Whenthe porous beads are submerged in aqueous or other solutions, the poresare infiltrated with the solutions. The beads have a distribution ofshapes that are approximately spherical on average with a 1.0 mm averagediameter.

The porous ion exchange beads are created by combining three components:ion exchange particles, a polymer, and a removable filler material. Thefiller material is potassium sulfate. The three components are mixedtogether using a solvent mixture of n-methyl-2-pyrrolidone, ethanol, andwater, and then the solvent is removed. The resulting mixture is groundand formed into beads using a mechanical press. The beads are heated toalter the structure of the polymer and improve mechanical strength. Thefiller is removed using water, which dissolves the filler and therebyleaves behind pores throughout the bead. The bead is heated again toalter the structure of the polymer and further improve mechanicalstrength.

The ion exchange column is 3.0 meters in length and 1.0 meters indiameter. The column is loaded with a fixed bed of porous beads. 1.0 MHCl acid is pumped into the bottom of the column at a flow rate of 0.5bed volumes per hour to elute a LiCl solution out the top of the column.The pores in the beads allow the acid solution to penetrate into thebead and access the ion exchange particles. Therefore, the ion exchangeparticles can absorb hydrogen from the acid while releasing lithium intothe acid. The Li₄Mn₅O₁₂ active material is converted to a hydrogenatedstate with a hydrogen-rich composition Li_(4-x)H_(x)Mn₅O₁₂ where x maybe close to 2. The ZrO₂ coating allows diffusion of hydrogen and lithiumrespectively to and from the active material while providing aprotective barrier that limits dissolution of manganese and oxygen fromthe active material. The beads release lithium to yield a LiCl solutionwith a lithium concentration of approximately 0.8 M in solution. Lithiumrecovery from the column is monitored using pH measurements andelemental analysis. After lithium recovery, the column is flushed withwater.

Next, brine is pumped down through the column at a flow rate of 3.0 bedvolumes per hour. The beads absorb lithium while releasing hydrogen. Thepores in the beads allow the brine solution to penetrate into the beadand access the ion exchange particles. Therefore, the ion exchangeparticles can absorb lithium from the brine while releasing hydrogeninto the brine. The beads are converted from a hydrogenated state to alithiated state with a lithium-rich composition Li₄Mn₅O₁₂ where x may beclose to 0. Lithium uptake by the beads in the column is monitored usingpH measurements and elemental analysis. The brine exiting the column isadjusted to a neutral pH using NaOH and then reinjected into a brinereservoir. After lithium uptake, the column is flushed with water.

The column is operated by repeating the previously described steps ofacid and brine pumping in alternation. This column operation functionsto extract lithium from the brine and produce a concentrated LiClsolution. During column operation, the porous beads allow the acid andbrine solutions to penetrate into the beads and deliver hydrogen andlithium to the ion exchange particles. The ion exchange particles areprotected from dissolution and degradation due to the ZrO₂ surfacecoating, which provides a protective barrier.

The LiCl solution that is yielded from column operation is processedinto lithium raw materials including Li₂CO₃, LiOH, LiCl and Li metal.These lithium raw materials are sold for use in batteries, alloys, andother products.

Example 3: Porous Ion Exchange Beads with PVDF Matrix

Lithium was extracted from a brine using porous ion exchange beads. Thebrine was an aqueous chloride solution containing 500 ppm Li, 60,000 ppmNa, 17,000 ppm Ca, and 3,000 ppm Mg. The porous ion exchange beads arecomprised of ion exchange particles and a polymer matrix. The ionexchange particles were comprised of a Li₄Mn₅O₁₂ core with a SiO₂coating. The particles were approximately spherical with a mean diameterof 40 microns, and the coating thickness was approximately 2 microns.The polymer matrix was comprised of polyvinylidene difluoride (PVDF).The porous beads contained pores with a distribution of pore sizesproviding diffusion channels from the bead surface into the beadinterior and to the ion exchange particles. When the porous beads weresubmerged in aqueous or other solutions, the pores were infiltrated withthe solutions. The beads had a distribution of shapes that areapproximately spherical on average with a 800 micron average diameter.

The porous ion exchange beads were created by combining threecomponents: the ion exchange particles, PVDF polymer, and a removablefiller material. The filler material was finely ground sodium chloride.The three components were mixed together using a dry mixer. Theresulting mixture was compacted into beads and fired at a temperature of190 Celcius to alter the structure of the polymer and improve mechanicalstrength. The filler was then removed using water, which dissolved thefiller and thereby left behind pores throughout the beads. The beadswere heated again to alter the structure of the polymer and furtherimprove mechanical strength.

The porous beads were treated with HCl acid to yield LiCl in solution.1.0 g of the beads were stirred in 30 mL of 1.0 M HCl acid for 1 hour atroom temperature. The pores in the beads allowed the acid solution topenetrate into the bead and access the ion exchange particles.Therefore, the ion exchange particles absorbed protons from the acidwhile releasing lithium into the acid solution. The Li₄Mn₅O₁₂ activematerial was converted to a protonated state with a hydrogen-richcomposition Li_(4-x)H_(x)Mn₅O₁₂ where x was close to 4. The SiO₂ coatingallowed diffusion of hydrogen and lithium respectively to and from theactive material while providing a protective barrier that limiteddissolution of manganese and oxygen from the active material. After 4hours of stirring, the solution was collected for elemental analysis tomeasure lithium yield.

After treatment in acid, the protonated beads were treated with brinewherein the particles absorbed lithium while releasing protons. Theprotonated beads were stirred in 200 mL of brine for 4 hours at roomtemperature. The pores in the beads allowed the brine solution topenetrate into the bead and access the ion exchange particles. The ionexchange particles absorbed lithium from the brine while releasingprotons into the brine. A pH modulating setup was used to measure the pHof the brine and add a solution of NaOH to neutralize the protonsreleased by the beads. The beads were converted from a protonated stateto a lithiated state with a lithium-rich composition Li_(4-x)H_(x)Mn₅O₁₂where x was approximately 0.5. After 4 hours of stirring, the solutionwas collected for elemental analysis to measure lithium uptake.

The lithiated beads were then treated again with acid to yield lithiumin solution as described previously. The cycle of protonation andlithiation was repeated to extract lithium from the brine and yield aLiCl solution. The pores in the beads facilitated penetration of theacid and brine solutions into the beads, facilitating absorption andrelease of lithium and protons by the ion exchange particle. Dissolutionand degradation of the active material in acid was limited due to theSiO₂ coating providing a protective barrier. Dissolution of the activematerial was measured with elemental analysis of the acid solutionfollowing stirring.

Example 4: Porous Ion Exchange Beads with Polystyrene Matrix

Lithium was extracted from a brine using porous ion exchange beads. Thebrine was an aqueous chloride solution containing approximately 100 ppmLi. The porous ion exchange beads were comprised of ion exchangeparticles and a polymer matrix. The ion exchange particles werecomprised of a Li₄Mn₅O₁₂. The particles were granular with an averagecharacteristic size of approximately 120 microns. The polymer matrix wascomprised of polystyrene. The beads contained 90 wt % ion exchangeparticles and 10 wt % polymer matrix. The porous beads contained poreswith a distribution of pore sizes providing diffusion channels from thebead surface into the bead interior and to the ion exchange particles.When the porous beads were submerged in aqueous or other solutions, thepores were infiltrated with the solutions.

The porous ion exchange beads were created by mixing polystyrene powderin acetone to partly dissolve the polystyrene. Then, theacetone-polystyrene mixture was mixed with the ion exchange particles.The mixture was then heated to remove the acetone, creating a porousmass. The removal of the acetone left behind pores that allowed fordiffusion of lithium ions and protons into the porous structure. Theporous mass was then ground into granules approximately 300 microns insize.

The porous beads were stirred for 1 hour with 0.75 N HCl acid to yieldLiCl in solution. The pores in the beads allowed the acid solution topenetrate into the bead and access the ion exchange particles.Therefore, the ion exchange particles absorbed protons from the acidwhile releasing lithium into the acid solution.

After treatment in acid, the protonated beads were treated with brinewherein the particles absorbed lithium while releasing protons. Theprotonated beads were stirred in brine for 4 hours at room temperature.The pores in the beads allowed the brine solution to penetrate into thebead and access the ion exchange particles. The ion exchange particlesabsorbed lithium from the brine while releasing protons into the brine.A pH modulating setup was used to measure the pH of the brine and add asolution of NaOH to neutralize the protons released by the beads.

The lithiated beads were then treated again with acid to yield lithiumin solution as described previously. The cycle of protonation andlithiation was repeated to extract lithium from the brine and yield aLiCl solution. The pores in the beads facilitated penetration of theacid and brine solutions into the beads, facilitating absorption andrelease of lithium and protons by the ion exchange particle.

Example 5: Lithium Extraction Using Porous Ion Exchange Beads in aStirred Tank Reactor with a Porous Mesh Compartment

Lithium is extracted from a brine using porous ion exchange beads. Thebrine is an aqueous chloride solution containing approximately 300 ppmLi. The porous ion exchange beads are comprised of ion exchangeparticles and a polymer matrix. The ion exchange particles are comprisedof a Li₄MnO₁₂. The particles are granular with an average characteristicsize of approximately 40 microns. The polymer matrix is comprised ofpolyvinylidene difluoride (PVDF). The beads contain approximately 80 wt% ion exchange particles and 20 wt % PVDF. The porous beads containpores with a distribution of pore sizes providing diffusion channelsfrom the bead surface into the bead interior and to the ion exchangeparticles. When the porous beads are submerged in aqueous or othersolutions, the pores are infiltrated with the solutions. The beads havea distribution of shapes that are approximately spherical on averagewith an 80 micron average diameter.

The porous ion exchange beads are created by dry-mixing PVDF powder withthe ion exchange particles and finely ground sodium chloride. Themixture is pressed into beads and is then heated to 200 C to melt thePVDF. Then the beads are washed with water to remove the sodium chlorideand create a porous bead.

The porous beads are loaded into a stirred tank reactor containing acompartment formed with a porous polymer mesh at the bottom of thecompartment that contains the beads in the stirred tank reactor whileallowing fluids to drain out of the bottom of the tank (FIG. 4 ). Thecompartment is open on the top and contains approximately 99% of thevolume of the stirred tank reactor. The beads are stirred for 1 hourwith 0.75 N HCl acid to yield LiCl in solution. The pores in the beadsallow the acid solution to penetrate into the bead and access the ionexchange particles. Therefore, the ion exchange particles absorb protonsfrom the acid while releasing lithium into the acid solution. The acidsolution is drained out of the bottom of the stirred tank reactors whilethe porous beads are contained above the porous mesh.

After treatment in acid, the protonated beads are treated with brinewherein the particles absorb lithium while releasing protons. Theprotonated beads are stirred in brine for 4 hours at room temperature.The pores in the beads allow the brine solution to penetrate into thebead and access the ion exchange particles. The ion exchange particlesabsorb lithium from the brine while releasing protons into the brine. ApH modulating setup is used to measure the pH of the brine and add asolution of NaOH to neutralize the protons released by the beads.

The lithiated beads are then treated again with acid to yield lithium insolution as described previously. The cycle of protonation andlithiation is repeated to extract lithium from the brine and yield aLiCl solution. The pores in the beads facilitate penetration of the acidand brine solutions into the beads, facilitating absorption and releaseof lithium and protons by the ion exchange particle.

Example 6: Lithium Extraction Using Porous Ion Exchange Beads in aColumn

Lithium was extracted from a brine using an ion exchange column loadedwith a fixed bed of porous ion exchange particles. The brine was anatural chloride solution containing approximately 100 ppm Li with otherchloride salts near saturation. The porous ion exchange beads werecomprised of ion exchange particles and a polymer matrix. The ionexchange particles were comprised of a Li₄MnO₁₂ with a radius ofapproximately 40 microns. The polymer matrix is comprised ofpolyvinylidene difluoride (PVDF). The porous beads were formed by drymixing PVDF powder with the ion exchange particles and finely groundsodium chloride. The mixture was heated to 180 C to melt the PVDF andform a polymer matrix to hold the bead together. The mixture then formeda bulk composite, which was reduced in size to form beads with irregularshape that were approximately 1 mm in size. Then, the sodium chloridewas washed from the composite to form a porous structure facilitatingdiffusion of fluids into the beads. The porous beads contained poreswith a distribution of pore sizes providing diffusion channels from thebead surface into the bead interior and to the ion exchange particles.When the porous beads were submerged in aqueous or other solutions, thepores were infiltrated with the solutions. The beads had a distributionof shapes with a typical size of approximately 1 mm.

The ion exchange column was 0.5 meters in length and 0.5 inches indiameter. The column was loaded with a fixed bed of porous beads. 1.0 MHCl acid was pumped into the bottom of the column to elute a LiClsolution out the top of the column. The pores in the beads allowed theacid solution to penetrate into the bead and access the ion exchangeparticles. Therefore, the ion exchange particles absorbed protons fromthe acid while releasing lithium into the acid. After elution, thecolumn was flushed with water.

Next, brine was pumped down through the column. The beads absorbedlithium while releasing hydrogen. The pores in the beads allowed thebrine solution to penetrate into the beads and access the ion exchangeparticles. Therefore, the ion exchange particles absorbed lithium fromthe brine while releasing protons into the brine. The beads wereconverted from a protonated state to a lithiated state. Lithium uptakeby the beads in the column was monitored using pH measurements andelemental analysis. After lithium uptake, the column was flushed withwater.

The column was operated by repeating the previously described steps ofacid and brine pumping in alternation. This column operation functionedto extract lithium from the brine and produce a concentrated LiClsolution. During column operation, the porous beads allowed the acid andbrine solutions to penetrate into the beads and deliver hydrogen andlithium to the ion exchange particles.

While preferred embodiments of the present invention have been shown anddescribed herein, it will be obvious to those skilled in the art thatsuch embodiments are provided by way of example only. Numerousvariations, changes, and substitutions will now occur to those skilledin the art without departing from the invention. It should be understoodthat various alternatives to the embodiments of the invention describedherein may be employed in practicing the invention. It is intended thatthe following claims define the scope of the invention and that methodsand structures within the scope of these claims and their equivalents becovered thereby.

What is claimed is:
 1. A method of extracting lithium from a liquidresource, comprising: i.) contacting a porous ion exchange bead with afirst acid solution to produce a protonated porous ion exchange bead;ii.) contacting the protonated porous ion exchange bead with a liquidresource to produce a lithiated porous ion exchange bead; and iii.)treating the lithiated porous ion exchange bead with the first acidsolution or a second acid solution to produce a salt solution comprisinglithium ions, wherein the porous ion exchange bead comprises ionexchange material, wherein the ion exchange material is selected fromcoated ion exchange particles, uncoated ion exchange particles, andcombinations thereof.
 2. The method of claim 1, wherein the liquidresource is a natural brine, a dissolved salt flat, seawater,concentrated seawater, a desalination effluent, a concentrated brine, aprocessed brine, waste brine from a bromine-extraction process, anoilfield brine, a liquid from an ion exchange process, a liquid from asolvent extraction process, a synthetic brine, a leachate from an ore orcombination of ores, a leachate from a mineral or combination ofminerals, a leachate from a clay or combination of clays, a leachatefrom recycled products, a leachate from recycled materials, orcombinations thereof.
 3. The method of claim 1, wherein the acidsolution comprises hydrochloric acid, sulfuric acid, phosphoric acid,hydrobromic acid, chloric acid, perchloric acid, nitric acid, formicacid, acetic acid, or combinations thereof.
 4. The method of claim 3,wherein the acid solution comprises hydrochloric acid, sulfuric acid,nitric acid, or combinations thereof.
 5. The method of claim 1, whereinthe porous ion exchange beads have an average diameter of less than 20mm.
 6. The method of claim 1 wherein the coated ion exchange particlesor uncoated ion exchange particles have an average diameter of less than100,000 nm.
 7. The method of claim 1, further comprising flushing theporous ion exchange bead, the protonated porous ion exchange bead, orthe lithiated porous ion exchange bead with water.
 8. The method ofclaim 1, wherein the method is conducted in a column or a stirred tankreactor.
 9. The method of claim 8, wherein the method is conducted in astirred tank reactor.
 10. The method of claim 8, wherein the method isconducted in a column.
 11. The method of claim 1, wherein the method isconducted in a plurality of vessels that are in fluid communication witheach other.
 12. The method of claim 1, wherein the porous ion exchangebeads perform the ion exchange reaction repeatedly over 10 cycles. 13.The method of claim 1, wherein the porous ion exchange beads perform theion exchange reaction repeatedly over 1,000 cycles.
 14. The method ofclaim 1, wherein the salt solution comprising lithium ions has aconcentration of lithium cations of less than 10 M.
 15. The method ofclaim 1, wherein the coated ion exchange particles comprise a coatingmaterial.
 16. The method of claim 15, wherein the coating materialcomprises a carbide, a nitride, an oxide, a phosphate, a fluoride, apolymer, carbon, a carbonaceous material, or combinations thereof. 17.The method of claim 15, wherein the coating material is selected fromthe group consisting of TiO₂, ZrO₂, MoO₂, SnO₂, Nb₂O₅, Ta₂O₅, SiO₂,Li₂ZrO₃, Li₂SiO₃, Li₂MoO₃, LiNbO₃, LiTaO₃, A₁PO₄, LaPO₄, ZrP₂O₇, MoP₂O₇,Mo₂P₃O₁₂, BaSO₄, A₁F₃, SiC, TiC, ZrC, Si₃N₄, ZrN, BN, carbon, graphiticcarbon, amorphous carbon, hard carbon, diamond-like carbon, solidsolutions thereof, and combinations thereof.
 18. The method of claim 15,wherein the coating material is selected from the group consisting ofpolyethylene, low density polyethylene, high density polyethylene,polypropylene, polyphenylene sulfide, polyester,polytetrafluoroethylene, types of polyamide, polyether ether ketone,polysulfone, polyvinylidene difluoride, poly (4-vinylpyridine-co-styrene), polystyrene, polybutadiene, acrylonitrilebutadiene styrene, polyvinyl chloride, polyvinylidene dichloride,ethylene tetrafluoroethylene polymer, poly(chlorotrifluoroethylene),ethylene chlorotrifluoro ethylene, polyvinyl fluoride, fluorinatedethylene-propylene, perfluorinated elastomer,chlorotrifluoroethylenevinylidene fluoride, perfluoropolyether,perfluorosulfonic acid, polyethylene oxide, polyethylene glycol, sodiumpolyacrylate, polyethylene-block-poly(ethylene glycol),polyacrylonitrile, polychloroprene (neoprene), polyvinyl butyral,expanded polystyrene, polydivinylbenzene,tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer, copolymers thereof, and combinations thereof.
 19. The methodof claim 1, wherein the ion exchange material comprises an oxide, aphosphate, an oxyfluoride, a fluorophosphate, or combinations thereof.20. The method of claim 1, wherein the ion exchange material is selectedfrom the group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂, Li₂TiO₃, Li₂MnO₃,Li₂SnO₃, LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂, LiTiO₂, Li₄TiO₄,Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄, Li₂CuP₂O₇, andLiCl.xAl(OH)₃.yH₂O, solid solutions thereof, and combinations thereof;wherein x is from 0.1-10; and y is from 0.1-10.